Intrinsic Enzyme-like Activity Research Articles

Organophosphorus Hydrolase-like Nanozyme with an Activity-Quenched Aggregation-Induced Emission Effect: A Self-Reporting and Specific Assay of Nerve Agents.

Given the promising prospect of aggregation-induced emission luminogens (AIEgens) in fluorescence assays, it is interesting and significant to endow AIEgens with molecular recognition capability (such as enzyme-like activity). Here, an AIE nanomaterial with intrinsic enzyme-like activity (named as "AIEzyme") is designed and synthesized via a facile coordination polymerization of Zr4+ and AIE ligands. AIEzyme possesses enhanced and stable fluorescence in different solvents because of the AIE effect of ligands in the rigid structure of a coordination polymer. On the other hand, the organophosphorus hydrolase (OPH)-mimicking activity of AIEzyme exhibits excellent affinity and specific activity. Interestingly, the OPH-like activity can quench the inherent fluorescence of AIEzyme by the hydrolysate of a typical organophosphorus nerve agent (OPNA), diethyl-4-nitrophenylphosphate. Due to the sensitive activity-induced quenching effect for AIE, the self-reporting fluorescence assay method based on AIEzyme was established, which shows ultrahigh sensitivity, high selectivity, good storage stability, and acceptable reliability for a real sample assay. Moreover, the simultaneous colorimetric method broadens the detection range and the application scenarios. The proposed assay method avoided the interference of O2 during detection because the OPH-like activity does not derive from the generation of ROS. As a bonus, AIEzyme can also be used for the degradation of OPNAs by OPH-like activity, and the process can be self-monitored by AIE quenching. This work would provide a new opportunity for expanding the application of AIEgens and artificial enzymes by endowing AIEgens with enzyme-like activity.

Exploring Nanozymes for Organic Substrates: Building Nano-organelles.

Since the discovery of the first peroxidase nanozyme (Fe3O4), numerous nanomaterials have been reported to exhibit intrinsic enzyme-like activity toward inorganic oxygen species, such as H2O2, oxygen, and O2 -. However, the exploration of nanozymes targeting organic compounds holds transformative potential in the realm of industrial synthesis. This review provides a comprehensive overview of the diverse types of nanozymes that catalyze reactions involving organic substrates and discusses their catalytic mechanisms, structure-activity relationships, and methodological paradigms for discovering new nanozymes. Additionally, we propose a forward-looking perspective on designing nanozyme formulations to mimic subcellular organelles, such as chloroplasts, termed "nano-organelles". Finally, we analyze the challenges encountered in nanozyme synthesis, characterization, nano-organelle construction and applications while suggesting directions to overcome these obstacles and enhance nanozyme research in the future. Through this review, our goal is to inspire further research efforts and catalyze advancements in the field of nanozymes, fostering new insights and opportunities in chemical synthesis.

Nanozymes for biomedical applications: Multi-metallic systems may improve activity but at the cost of higher toxicity?

Nanozymes are nanomaterials with intrinsic enzyme-like activity with selected advantages over native enzymes such as simple synthesis, controllable activity, high stability, and low cost. These materials have been explored as surrogates to natural enzymes in biosensing, therapeutics, environmental protection, and many other fields. Among different nanozymes classes, metal- and metal oxide-based nanozymes are the most widely studied. In recent years, bi- and tri-metallic nanomaterials have emerged often showing improved nanozyme activity, some of which even possess multifunctional enzyme-like activity. Taking this concept even further, high-entropy nanomaterials, that is, complex multicomponent alloys and ceramics like oxides, may potentially enhance activity even further. However, the addition of various elements to increase catalytic activity may come at the cost of increased toxicity. Since many nanozyme compositions are currently being explored for in vivo biomedical applications, such as cancer therapeutics, toxicity considerations in relation to nanozyme application in biomedicine are of vital importance for translation. This article is categorized under: Therapeutic Approaches and Drug Discovery > Emerging Technologies Toxicology and Regulatory Issues in Nanomedicine > Toxicology of Nanomaterials Diagnostic Tools > Diagnostic Nanodevices.

Propelling gold nanozymes: catalytic activity and biosensing applications.

Recently, gold nanomaterials have been rapidly developed owing to their high stability, good biocompatibility, and multifunctionality. The unique catalytic activity of gold nanomaterials has driven the emergence of the concept for a"gold nanozyme." Understanding the characteristics of gold nanozymes is crucial for improving their catalytic performance as well as expanding their applications. In this review, we provide an overview of the intrinsic enzyme-like activities of gold nanozymes, including peroxidase-, catalase-, superoxide dismutase-, and glucose oxidase-like activities, and the catalytic mechanisms involved. In addition, strategies for modulating the catalytic activity of gold nanozymesand theirapplications in biosensing were discussed in detail. Moreover, we highlight the current challenges of gold nanozymes and look forward to attracting more attention for propelling the developments in this field.

Multisignal Biosensors Based on Mn Paramagnetic Relaxation and Nanocatalysis for Norovirus Detection.

A multisignal method for the sensitive detection of norovirus based on Mn paramagnetic relaxation and nanocatalysis was developed. This dual-modality sensing platform was based on the strong relaxation generated by cracked Au@MnO2 nanoparticles (NPs) and their intrinsic enzyme-like activity. Ascorbic acid rapidly cracked the MnO2 layer of Au@MnO2 NPs to release Mn(II), resulting in the relaxation modality being in a "switch-on" state. Under the optimal conditions, the relaxation modality exhibited a wide working range (6.02 × 103-3.01 × 107 copies/μL) and a limit of detection (LOD) of 2.29 × 103 copies/μL. Using 4,4',4″,4″'-(porphine-5,10,15,20-tetrayl) tetrakis (benzenesulfonic acid) (tpps)-β-cyclodextrin (tpps-β-CD) as a T1 relaxation signal amplification reagent, a lower LOD was obtained. The colorimetric modality exploited the "peroxidase/oxidase-like" activity of Au@MnO2 NPs, which catalyzed the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB, which exhibited a working range (6.02 × 104-6.02 × 106 copies/μL) and an LOD of 2.6 × 104 copies/μL. In addition, the rapid amplification reaction of recombinase polymerase enabled the detection of low norovirus levels in food samples and obtained a working range of 101-106 copies/mL and LOD of 101 copies/mL (relaxation modality). The accuracy of the sensor in the analysis of spiked samples was consistent with that of the real-time quantitative reverse transcription polymerase chain reaction, demonstrating the high accuracy and practical utility of the sensor.

Enhanced the intrinsic oxidase-like activity of chiral carbon dots via manganese doping for selective catalytic oxidation

It is highly desirable to design and construct chemical catalysts with high activity and specificity as the alternatives of natural enzymes for industrial application. Chiral carbon dots (CDs), possessing both the intrinsic enzyme-like activity and specific recognition ability, are one of good candidates for enzyme-like catalysts. However, their catalytic activity is far from that of natural enzymes and needs to be enhanced. In this work, the modulation of the chiral structure and catalytic activity of chiral CDs with intrinsic oxidase-like activity was implemented by manganese (Mn) doping. Under the light condition, chiral CDs (l-Ser-CDs and d-Ser-CDs) derived from chiral serine (Ser) show weak catalytic activity and low selectivity toward the oxidation of L type of dopamine (l-DOPA), whereas the Mn functionalized chiral CDs (l-Mn-CDs or d-Mn-CDs) exhibit 6.9 times higher in catalytic activity and 2.9 times in selectivity ratio (SR) than Ser-CDs. Mn-CDs involve two-path catalytic process, in which the photogenerated electrons could reduce O2 to O2− as the active species and the holes would oxidize DOPA directly. Moreover, doping of Mn enables the CDs to generate more O2−. Besides, l-Mn-CDs have higher catalytic activity than that of d-Mn-CDs (+54.2 %), and the chiral Mn-CDs have stronger selective adsorption capacity towards chiral DOPA than Ser-CDs. Our work provides a new method for designing and preparing novel chiral artificial enzymes.

Nanoenzymes: A Radiant Hope for the Early Diagnosis and Effective Treatment of Breast and Ovarian Cancers.

Breast and ovarian cancers, despite having chemotherapy and surgical treatment, still have the lowest survival rate. Experimental stages using nanoenzymes/nanozymes for ovarian cancer diagnosis and treatment are being carried out, and correspondingly the current treatment approaches to treat breast cancer have a lot of adverse side effects, which is the reason why researchers and scientists are looking for new strategies with less side effects. Nanoenzymes have intrinsic enzyme-like activities and can reduce the shortcomings of naturally occurring enzymes due to the ease of storage, high stability, less expensive, and enhanced efficiency. In this review, we have discussed various ways in which nanoenzymes are being used to diagnose and treat breast and ovarian cancer. For breast cancer, nanoenzymes and their multi-enzymatic properties can control the level of reactive oxygen species (ROS) in cells or tissues, for example, oxidase (OXD) and peroxidase (POD) activity can be used to generate ROS, while catalase (CAT) or superoxide dismutase (SOD) activity can scavenge ROS. In the case of ovarian cancer, most commonly nanoceria is being investigated, and also when folic acid is combined with nanoceria there are additional advantages like inhibition of beta galactosidase. Nanocarriers are also used to deliver small interfering RNA that are effective in cancer treatment. Studies have shown that iron oxide nanoparticles are actively being used for drug delivery, similarly ferritin carriers are used for the delivery of nanozymes. Hypoxia is a major factor in ovarian cancer, therefore MnO2-based nanozymes are being used as a therapy. For cancer diagnosis and screening, nanozymes are being used in sonodynamic cancer therapy for cancer diagnosis and screening, whereas biomedical imaging and folic acid gold particles are also being used for image guided treatments. Nanozyme biosensors have been developed to detect ovarian cancer. This review article summarizes a detailed insight into breast and ovarian cancers in light of nanozymes-based diagnostic and therapeutic approaches.

Synergistic antibacterial therapy for multidrug-resistant bacterial infections using multifunctional nanozymes

Multidrug-resistant (MDR) bacterial infections have become major threats to public health worldwide. To address this challenge, nanozyme with intrinsic enzyme-like activity has been used that can serve as broad-spectrum antibiotics. However, the efficacy of individual nanozyme is hindered by its limited catalytic activity and therapeutic efficiency. In this study, we develop broad-spectrum antibacterial nanocomposites, namely IrOx@PDA NPs-RSNO (IP NPs-RSNO), which demonstrate remarkable efficacy in eradicating MDR bacteria. The excellent antibacterial performance of IP NPs-RSNO is attributed to the synergistic effects of NIR photothermal property, NIR-enhanced peroxidase-like (POD-like) activity, and NIR-triggered release of NO. IP NPs-RSNO can effectively eliminate carbapenem-resistant Escherichia coli (CREC) and methicillin-resistant Staphylococcus aureus (MRSA), showing excellent therapeutic performance in treating MRSA-infected wounds. This work provides insights into the design of multifunctional nanozymes for antibacterial applications.

A Covalent Organic Framework Derived N-doped Carbon Nanozyme as the All-rounder for Targeted Catalytic Therapy and NIR-II Photothermal Therapy of Cancer.

Nanomaterials with intrinsic enzyme-like activities (nanozymes) have gained significant attention in cancer catalytic therapy; however, developing metal-free nanozymes with multivariant enzyme-like activity as the "all-rounder" for cancer therapy remains challenging. Herein, a covalent organic framework (COF) derived carbon-based nanozyme is rationally devised to achieve synergistic catalytic therapy and second near-infrared (NIR-II) photothermal therapy of cancer. The developed nanozyme possesses multivariant enzyme-like activities, including oxidase (OXD)-like, catalase (CAT)-like, and peroxidase (POD)-like catalytic activities, which enables the nanozyme to produce adequate reactive oxygen species (ROS) for cancer cell killing. Furthermore, the nanozyme showed excellent photothermal converting activity that could kill cancer cells upon NIR-II laser irradiation, owing to the strong NIR-II absorption capacity of carbon-based materials. It is also worth noting that the nanozyme exhibited cytotoxicity specifically in tumor tissue profiting from the discrepant H2O2 level between tumor and normal tissue and the spatiotemporal controllability of laser irradiation. This work may inspire further development of intelligent nanozymes in biological applications across broad therapeutic and biomedical fields.

Nanozymes With Osteochondral Regenerative Effects: An Overview of Mechanisms and Recent Applications.

With the discovery of the intrinsic enzyme-like activity of metal oxides, nanozymes garner significant attention due to their superior characteristics, such as low cost, high stability, multi-enzyme activity, and facile preparation. Notably, in the field of biomedicine, nanozymes primarily focus on disease detection, antibacterial properties, antitumor effects, and treatment of inflammatory conditions. However, the potential for application in regenerative medicine, which primarily addresses wound healing, nerve defect repair, bone regeneration, and cardiovascular disease treatment, is garnering interest as well. This review introduces nanozymes as an innovative strategy within the realm of bone regenerative medicine. The primary focus of this approach lies in the facilitation of osteochondral regeneration through the modulation of the pathological microenvironment. The catalytic mechanisms of four types of representative nanozymes are first discussed. The pathological microenvironment inhibiting osteochondral regeneration, followed by summarizing the therapy mechanism of nanozymes to osteochondral regeneration barriers is introduced. Further, the therapeutic potential of nanozymes for bone diseases is included. To improve the therapeutic efficiency of nanozymes and facilitate their clinical translation, future potential applications in osteochondral diseases are also discussed and some significant challenges addressed.

Nitrogen-doped porous carbon nanomaterials synthesized using a magadiite template as efficient peroxidase mimics for colorimetric detection of ascorbic acid as an antioxidant.

Nanomaterials with intrinsic enzyme-like activity have gained substantial scientific attention as viable substitutes to natural biological enzymes owing to their cheap price and great stability. Numerous artificial enzyme mimics have been employed effectively in sectors such as sensing, environmental processing, and cancer treatment. In this study, novel nitrogen-doped porous carbon nanomaterials (CPs) were produced by modifying polypyrrole with magadiite using chemical oxidative polymerization and calcination methods. The obtained nitrogen-doped porous carbon nanomaterials exhibited improved peroxidase-like activity, which catalyzed the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2) to produce colorful compounds. Kinetic investigation revealed that the affinity for TMB of nitrogen-doped porous carbon peroxidase mimics was higher than that of genuine horseradish peroxidase (HRP). In addition, a sensitive assay with encouraging performance for the colorimetric detection of ascorbic acid (AA) was successfully fabricated employing nitrogen-doped porous carbon nanomaterials as peroxidase mimics. The results were satisfactory and demonstrated its potential application in antioxidant detection.

Nanozymes with Peroxidase-like Activity for Ferroptosis-Driven Biocatalytic Nanotherapeutics of Glioblastoma Cancer: 2D and 3D Spheroids Models.

Glioblastoma (GBM) is the most common primary brain cancer in adults. Despite the remarkable advancements in recent years in the realm of cancer diagnosis and therapy, regrettably, GBM remains the most lethal form of brain cancer. In this view, the fascinating area of nanotechnology has emerged as an innovative strategy for developing novel nanomaterials for cancer nanomedicine, such as artificial enzymes, termed nanozymes, with intrinsic enzyme-like activities. Therefore, this study reports for the first time the design, synthesis, and extensive characterization of innovative colloidal nanostructures made of cobalt-doped iron oxide nanoparticles chemically stabilized by a carboxymethylcellulose capping ligand (i.e., Co-MION), creating a peroxidase-like (POD) nanozyme for biocatalytically killing GBM cancer cells. These nanoconjugates were produced using a strictly green aqueous process under mild conditions to create non-toxic bioengineered nanotherapeutics against GBM cells. The nanozyme (Co-MION) showed a magnetite inorganic crystalline core with a uniform spherical morphology (diameter, 2R = 6-7 nm) stabilized by the CMC biopolymer, producing a hydrodynamic diameter (HD) of 41-52 nm and a negatively charged surface (ZP~-50 mV). Thus, we created supramolecular water-dispersible colloidal nanostructures composed of an inorganic core (Cox-MION) and a surrounding biopolymer shell (CMC). The nanozymes confirmed the cytotoxicity evaluated by an MTT bioassay using a 2D culture in vitro of U87 brain cancer cells, which was concentration-dependent and boosted by increasing the cobalt-doping content in the nanosystems. Additionally, the results confirmed that the lethality of U87 brain cancer cells was predominantly caused by the production of toxic cell-damaging reactive oxygen species (ROS) through the in situ generation of hydroxyl radicals (·OH) by the peroxidase-like activity displayed by nanozymes. Thus, the nanozymes induced apoptosis (i.e., programmed cell death) and ferroptosis (i.e., lipid peroxidation) pathways by intracellular biocatalytic enzyme-like activity. More importantly, based on the 3D spheroids model, these nanozymes inhibited tumor growth and remarkably reduced the malignant tumor volume after the nanotherapeutic treatment (ΔV~40%). The kinetics of the anticancer activity of these novel nanotherapeutic agents decreased with the time of incubation of the GBM 3D models, indicating a similar trend commonly observed in tumor microenvironments (TMEs). Furthermore, the results demonstrated that the 2D in vitro model overestimated the relative efficiency of the anticancer agents (i.e., nanozymes and the DOX drug) compared to the 3D spheroid models. These findings are notable as they evidenced that the 3D spheroid model resembles more precisely the TME of "real" brain cancer tumors in patients than 2D cell cultures. Thus, based on our groundwork, 3D tumor spheroid models might be able to offer transitional systems between conventional 2D cell cultures and complex biological in vivo models for evaluating anticancer agents more precisely. These nanotherapeutics offer a wide avenue of opportunities to develop innovative nanomedicines for fighting against cancerous tumors and reducing the frequency of severe side effects in conventionally applied chemotherapy-based treatments.

Photothermal Enhanced and Tumor Microenvironment Responsive Nanozyme for Amplified Cascade Enzyme Catalytic Therapy.

Nanocatalysts, a class of nanomaterials with intrinsic enzyme-like activities, have been widely investigated for cancer catalytic therapy in recent years. However, precise construction of nanocatalysts with excellent enzyme catalytic activity and biosafety for tumor therapy still remains challenging. Here, a biodegradable nanocatalyst, PEGylated Cux Mny Sz (PCMS), is reported that can promote cascade catalytic reactions in tumor microenvironment (TME) while confining off-target side effects on normal tissues. PCMS not only catalyzes the cascade conversion of endogenous hydrogen peroxide (H2 O2 ) to oxygen (O2 ) via catalase-like activity and then to superoxide radical (·O2 - ) via oxidase-like activity in the TME, but also effectively depletes intracellular glutathione via glutathione oxidase-like activity. The cascade catalytic reactions, by taking advantage of high H2 O2 level in tumor cells, result in an enhanced enzyme catalytic effect in generation of ·O2 - . More importantly, PCMS exhibits prominent photothermal effect under NIR-II 1064nm laser irradiation that can further enhance chemodynamic therapy (CDT) efficacy in tumors. In addition, the biodegradation in TME and excellent photothermal effect of PCMS are beneficial to magnetic resonance imaging, photoacoustic imaging and infrared thermal imaging, resulting in tracing the fate of PCMS in vivo. This study provides a new tool for rational design of TME-responsive nanocatalysts with high biocompatibility for tumor catalytic therapy.

Construction of Zn-heptapeptide bionanozymes with intrinsic hydrolase-like activity for degradation of di(2-ethylhexyl) phthalate

Nanozyme with intrinsic enzyme-like activity has emerged as favorite artificial catalyst during recent years. However, current nanozymes are mainly limited to inorganic-derived nanomaterials, while biomolecule-sourced nanozyme (bionanozyme) are rarely reported. Herein, inspired by the basic structure of natural hydrolase family, we constructed 3 oligopeptide-based bionanozymes with intrinsic hydrolase-like activity by implementing zinc induced self-assembly of histidine-rich heptapeptides. Under mild condition, divalent zinc (Zn2+) impelled the spontaneous assembly of short peptides (i.e. Ac-IHIHIQI-CONH2, Ac-IHIHIYI-CONH2, and Ac-IHVHLQI-CONH2), forming hydrolase-mimicking bionanozymes with β-sheet secondary conformation and nanofibrous architecture. As expected, the resultant bionanozymes were able to hydrolyze a serious of p-nitrophenyl esters, including not only the simple substrate with short side-chain (p-NPA), but also more complicated ones (p-NPB, p-NPH, p-NPO, and p-NPS). Moreover, the self-assembled Zn-heptapeptide bionanozymes were also proven to be capable of degrading di(2-ethylhexyl) phthalate (DEHP), a typical plasticizer, showing great potential for environmental remediation. Based on this study, we aim to provide theoretical references and exemplify a specific case for directing the construction and application of bionanozyme.

Prussian Blue/Chitosan Micromotors with Intrinsic Enzyme-like Activity for (bio)-Sensing Assays

Prussian Blue (PB)/chitosan enzyme mimetic tubular micromotors are used here for on-the-fly (bio)-sensing assays. The micromotors are easily prepared by direct deposition of chitosan into the pores of a membrane template and in situ PB synthesis during hydrogel deposition. Under judicious pH control, PB micromotors display enzyme mimetic capabilities with three key functions on board: the autonomous oxygen bubble propulsion (with PB acting as a catalase mimic for hydrogen peroxide decomposition), 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation (with PB acting as a peroxidase mimic for analyte detection), and as a magnetic material (to simplify the (bio)-sensing steps). In connection with chitosan capabilities, these unique enzyme mimetic micromotors are further functionalized with acetylthiocholinesterase enzyme (ATChE) to be explored in fast inhibition assays (20 min) for the colorimetric determination of the nerve agent neostigmine, with excellent analytical performance in terms of quantification limit (0.30 μM) and concentration linear range (up to 500 μM), without compromising efficient micromotor propulsion. The new concept illustrated holds considerable potential for a myriad of (bio)-sensing applications, including forensics, where this conceptual approach remains to be explored. Micromotor-based tests to be used in crime scenes are also envisioned due to the reliable neostigmine determination in unpretreated samples.

On-Cell Catalytic Detection of Epithelial-to-Mesenchymal Transition by a Clusterzyme Bioprobe.

We construct a peptide-conjugated metal cluster as an enzyme-like catalytic bioprobe to enhance quantitative analysis of a membrane protein biomarker and detect epithelial-to-mesenchymal transition of tumor cells. This bioprobe with atomically precise formula, termed clusterzyme, possesses selective recognition and intrinsic enzyme-like activity. These favorable features facilitate sensitive quantitative analysis of the membrane protein in situ through on-cell catalytic signal amplification. This clusterzyme-based analytical method exhibits excellent compatibility with a traditional enzyme-linked immunosorbent assay and improved detection sensitivity with accuracy and robustness. Further, the expression level of the membrane protein reflects the ability of migration and invasion of model tumor cells, revealing epithelial-to-mesenchymal transition process. This work offers a facile and sensitive approach to monitor tumor cell type evolution at the molecular level, demonstrating a potential application of early cancer diagnosis and therapy assessment.

Biocatalytic Metal-Organic Frameworks: Promising Materials for Biosensing.

The highly efficient and specific catalysis of enzymes allows them to recognize a myriad of substrates, which enables biosensing. However, the fragility of natural enzymes severely restricts their practical applications. Metal-organic frameworks (MOFs) with porous networks and attractive functions have been intelligently employed as supports to encase enzymes and protect them against harsh environments. More importantly, customizable construction and composition affords the intrinsic enzyme-like activity of some MOFs (known as nanozymes), which provides an alternative route for the construction of robust enzyme mimics. This review will introduce the concept of these biocatalytic MOFs, with special emphasis on how biocatalytic processes that operate in these materials can reverse the plight of native enzyme-based biosensing. In addition, the present challenges and future outlooks in this research field are briefly discussed.

Bimetallic oxide Cu1.5Mn1.5O4 cage-like frame nanospheres with triple enzyme-like activities for bacterial-infected wound therapy

Copper-based nanomaterials with intrinsic enzyme-like activity have shown increasing potential as new broad-spectrum antibiotics. However, due to its low catalytic activity, poor glutathione (GSH) depletion capacity, and complex material design, their feasibility is still far from satisfactory. Herein, bimetallic oxide Cu1.5Mn1.5O4 cage-like frame nanospheres (CFNSs) were successfully prepared by a two-step approach for the first time, including gas-assisted soft template solvothermal preparation of Cu-Mn hydroxide hollow sphere (Cu-Mn-OH HSs) precursors, and then calcination to synthesize Cu1.5Mn1.5O4 CFNSs. This ingenious, simple, and rapid material synthesis strategy could obtain well-dispersed and extremely uniform Cu1.5Mn1.5O4 CFNSs with a special mesoporous cavity structure, making its performance close to the requirements of practical applications. Interestingly, the as-prepared Cu1.5Mn1.5O4 CFNSs showed enhanced triple enzyme-like activities (oxidase-, peroxidase-, and glutathione peroxidase-like), which could significantly promote the generation of reactive oxygen species (ROS) due to the increased exposure of active edge sites. Cu1.5Mn1.5O4 CFNSs could effectively kill bacteria by combining OXD-like, POD-like, and GSH-Px-like nanozyme activities. More importantly, in vivo wound healing showed that Cu1.5Mn1.5O4 CFNSs could be conveniently used for wound disinfection. In addition, Cu1.5Mn1.5O4 CFNSs exhibited excellent biosafety without observable toxicity or side effects in mice. This work emphasizes the potential application of bimetallic oxides with triple enzyme-like activities in antibacterial therapy.

MoS2 Nanosheets–Cyanobacteria Interaction: Reprogrammed Carbon and Nitrogen Metabolism

Fully understanding the environmental implications of engineered nanomaterials is crucial for their safe and sustainable use. Cyanobacteria, as the pioneers of the planet earth, play important roles in global carbon and nitrogen cycling. Here, we evaluated the biological effects of molybdenum disulfide (MoS2) nanosheets on a N2-fixation cyanobacteria (Nostoc sphaeroides) by monitoring growth and metabolome changes. MoS2 nanosheets did not exert overt toxicity to Nostoc at the tested doses (0.1 and 1 mg/L). On the contrary, the intrinsic enzyme-like activities and semiconducting properties of MoS2 nanosheets promoted the metabolic processes of Nostoc, including enhancing CO2-fixation-related Calvin cycle metabolic pathway. Meanwhile, MoS2 boosted the production of a range of biochemicals, including sugars, fatty acids, amino acids, and other valuable end products. The altered carbon metabolism subsequently drove proportional changes in nitrogen metabolism in Nostoc. These intracellular metabolic changes could potentially alter global C and N cycles. The findings of this study shed light on the nature and underlying mechanisms of bio-nanoparticle interactions, and offer the prospect of utilization bio-nanomaterials for efficient CO2 sequestration and sustainable biochemical production.

Sophisticated plasmon-enhanced photo-nanozyme for anti-angiogenic and tumor-microenvironment-responsive combinatorial photodynamic and photothermal cancer therapy

In the exploitation of nanozymes possessing intrinsic enzyme-like activities for cancer therapy, minor focus has been devoted to plasmonic nanostructures with localized surface plasmon resonance (LSPR)-driven properties. Here, we report the application of unique peroxidase-mimicking plasmonic photo-nanozymes coupling tumor-microenvironment-responsive reactive oxygen species generation with photothermal effect for effective combinatorial therapy. The well-defined anisotropic photo-nanozyme is synthesized by selectively depositing Pd nanoparticles on the tips of gold nanobypyramids. Intrinsic peroxidase-like properties with 1.5-fold-activity enhancement under photoexcitation are ascribed to a Pd-induced hot electrons/holes separation with efficient H2O2 decomposition. The LSPR-induced photocatalytic/photothermal combinatorial effects are remarkably enhanced upon H2O2 addition, critically suppressing the cell survival rate under near-infrared light. An effective decomposition of cell-signaling H2O2 additionally reveals prominent expression hindrance of vascular endothelial growth factor and hypoxia-inducible factor 1α. Our seminal findings uncover an interrelation between LSPR-induced phenomena and biomimetic fingerprints, valuable to overcome the shortcomings of conventional photodynamic therapy.